CN107583667A - A kind of assistant for calalytic cracking for improving octane number bucket and preparation method thereof - Google Patents
A kind of assistant for calalytic cracking for improving octane number bucket and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of assistant for calalytic cracking for improving octane number bucket and preparation method thereof, on the basis of the butt weight of the auxiliary agent, the auxiliary agent is included with the weight % of dry basis 10 75 phosphorous MFI structure molecular sieve, with the weight % of dry basis 3 40 phosphorus aluminium inorganic binder, in terms of oxide 1 30 weight % other inorganic binders, with the metallic addition selected from least one of VIII race's metal and manganese, zinc, gallium of the weight % of dry basis 0 60 the second clay, and in terms of oxide 0.5 15 weight %.Auxiliary agent provided by the invention is used for catalytic cracking process, octane number is improved by improving the content of isohydrocarbon in gasoline, while keeps yield of gasoline to be basically unchanged, and then improves octane number bucket.
Description
Technical field
The present invention relates to a kind of assistant for calalytic cracking for improving octane number bucket and preparation method thereof.
Background technology
In recent years, domestic motor vehicles recoverable amount persistently rises, and supports domestic gasoline terminal consumption demand to keep vigorous." ten
Two or five " automobile sales volume increases by 11% every year during, drives gasoline demand to keep average annual 5% steady growth, it is contemplated that to vapour in 2015
Oily Apparent con- sumption is up to 98Mt.Propylene production capacity is specially produced with a new round to go into operation, the coming five years whole world propylene supply will be big
The big growth for exceeding demand.It was predicted that the coming five years whole world propylene production capacity will increase 30Mt, and demand growth is estimated only
22Mt, dropped because this gap between Supply and Demand may result in propylene price.In the market demand and economic benefit
Promotion under, oil refining enterprise will take voluminous gasoline to produce the production decision of liquefied gas less.To realize the purpose of voluminous gasoline, one
Aspect can be adjusted to technological parameter, on the other hand can adjust catalyst formulation.
Required tight promotion to fuel mass by environmental regulation requirement and automobile industry, in recent years global motor petrol matter
Amount lifting is very rapid, and oil quality upgrading paces in China's are also substantially accelerated, and especially face state VI and discharge the formulation newly advised, high
Octane number, the clean gasoline of low alkene arene content turn into new oil-producing scheme.External gasoline pool compositing characteristic is：Catalytic cracking
Gasoline proportionality is relatively low, as U.S.'s FCC gasoline only accounts for 1/3 or so；Average RON is higher, about 93-94；Other antiknock components
More, the development of especially other antiknock component technologies constantly promotes the raising of octane number.But China's major oil
Quality still has certain gap compared with developed countries, and at present, it is total that China FCC (fluid catalytic cracking) gasoline accounts for motor petrol
More than the 70% of amount, Reformed Gasoline and other high-quality high octane gasoline component contents are too low, less than 9%, and low octane rating
Direct steaming gasoline proportion is higher, reaches about 13%.Therefore, the height of FCC gasoline octane rises to octane number aggregate level
Very important effect.The FCC gasoline octane (RON) in China is up to 90-92, minimum 87-88, average out to 89-90；
MON is up to 80.6, and minimum 78, average out to 79, larger difference compared with the quality of gasoline of some other developed country be present
Away from therefore, raising octane number, it is trend of the times to realize that gasoline upgrades.In addition, during gasoline cleaning, one
A little measures such as control content of olefin in gasoline, desulfurization, result in the different degrees of loss of octane number, the contradiction of octane number shortage will more
Add protrusion.
Gasoline isomerization is to improve an effective way of octane number.Due to isomeric olefine and isomeric alkane with side chain
Hydrocarbon has higher octane number than corresponding normal olefine, therefore the cracking additive containing high silica alumina ratio molecular sieve can be reduced suitably point
The lytic activity and hydrogen transfer activity of son sieve, while isomerization ability is improved, isomeric olefine and isoparaffin concentration increase in product
Add, it is possible to while octane number is improved, reduce the loss of yield of light oil.
Chinese patent CN 102851058A disclose a kind of method for improving catalytically cracked gasoline octane number, party's legal system
Alkene in gasoline can be changed into virtue by standby assistant for calalytic cracking using the ZSM-5 molecular sieve that framework si-al ratio is 30-150
Fragrant hydrocarbon, content of olefin in gasoline is reduced while octane number is improved.
Chinese patent CN 102049291A disclose a kind of high silica alumina ratio molecular sieve auxiliary agent using phosphorus aluminium glue as binding agent,
With higher intensity and activity, octane number is improved while improving product distribution.
After ZSM-5 zeolite is modified with phosphorus-containing compound, its cracking activity stability can improve, and reduce zeolite
Dosage.
Chinese patent CN 1611299A disclose a kind of phosphorous and MFI structure molecular sieve of metal component, its anhydrous chemical
Expression formula, it is calculated as with the weight of oxide：(0-0.3)Na2O(0.5-5.5)Al2O3(1.3-10)P2O5(0.7-15)M1xOy
(0.01-5)M2mOn(70-97)SiO2, the one kind of wherein M1 in transition-metal Fe, Co and Ni, M2 be selected from metal Zn, Mn,
Any of Ga and Sn.
Chinese patent CN 1057408A disclose a kind of catalyst for cracking containing silica-rich zeolite, and there is higher catalysis to split
Solution activity, wherein described silica-rich zeolite is containing 0.01-3.0 weight % phosphorus, 0.01-1.0 weight % iron or 0.01-10 weight % aluminium
ZSM-5, β zeolite or modenite, it is to add Hydrogen or potassium type ZSM-5 zeolite of the silica alumina ratio more than 15, β zeolites or modenite
Heat is to 350-820 DEG C, with 0.1-10 hours-1Volume space velocity be passed through the halide solution of aluminium, iron halide solution or
Obtained after saline solution of ammonium phosphate.
Disclosed in United States Patent (USP) USP5,110,776 with the preparation method of the ZSM-5 zeolite catalyst of P Modification.It is described
P Modification process be that zeolite is dispersed in the pH value 2-6 phosphorus-containing compound aqueous solution, then with matrix be beaten, spray drying
Shaping.Gained catalyst does not increase dry gas and coke yield while octane number is improved.
A kind of method for improving aperture and mesopore zeolite catalytic activity is disclosed in United States Patent (USP) USP6,080,303.The party
Method is to handle aperture and mesopore zeolite with phosphorus compound, then by phosphorus-treated zeolite and AlPO4Gel Compositions.This method
The activity and hydrothermal stability of aperture and mesopore zeolite can be improved.
At present, for most of catalytic cracking unit, on the premise of identical liquefied gas yield, liquefaction is improved
Density of propylene in gas is the important channel for improving catalytic cracking unit economic benefit.
A kind of phosphorous and rare earth and the zeolite with MFI structure are disclosed in Chinese patent CN 1147420A, its is anhydrous
It is aRE to learn composition2O3·bNa2O·Al2O3·cP2O5·dSiO2, wherein a=0.01-0.25, b=0.005-0.02, c=
0.2-1.0, d=35-120.The zeolite is for having excellent hydrothermal activity stability and good during hydro carbons pyrolytic conversion
Selectivity of light olefin.
United States Patent (USP) USP3,758,403 be more early disclosed in the method for ZSM-5 zeolite is added in catalytic cracking catalyst can be with
Improve the octane number and increase C of gasoline3-C4The yield of alkene.For example, in the conventional catalyst containing 10%REY addition from 1.5,
2.5th, after 5 to 10% ZSM-5 zeolite, octane number improves, the yield increase of low-carbon alkene；Using containing ZSM-5 zeolite
Also there is same effect during auxiliary agent.
Proposed in United States Patent (USP) USP 5,318,696 has MFI based on a kind of large pore zeolite and silica alumina ratio less than 30
The hydrocarbon conversion process process of the catalyst of the zeolite composition of structure.The technique produces higher octane by improved catalytic cracking process
It is worth gasoline, and increased low carbon olefine output, particularly propylene.
In the prior art, the raising of octane number is realized by producing in high-yield olefin and aromatic hydrocarbons mostly, not only makes yield of gasoline
Decrease, also do not meet the composition requirement of Novel clean gasoline.Therefore, technical staff wishes ensureing the same of yield of gasoline
When, produce high-knock rating gasoline.
The content of the invention
It is an object of the invention to provide a kind of assistant for calalytic cracking for improving octane number bucket and preparation method thereof, incite somebody to action this
The auxiliary agent that invention provides is used for catalytic cracking process, by improving the content of isohydrocarbon in gasoline so as to improve octane number,
Keep yield of gasoline to be basically unchanged simultaneously, and then improve octane number bucket.
To achieve these goals, the present invention provides a kind of assistant for calalytic cracking for improving octane number bucket, with described
On the basis of the butt weight of auxiliary agent, the auxiliary agent is included with dry basis 10-75 weight % phosphorous MFI structure molecular sieve, with
Dry basis 3-40 weight % phosphorus aluminium inorganic binder, the weight of the 1-30 in terms of oxide % other inorganic binders, with
Dry basis 0-60 weight % the second clay, and the weight of the 0.5-15 in terms of oxide % selected from VIII race's metal and manganese, zinc,
The metallic addition of at least one of gallium；Wherein, described phosphorus aluminium inorganic binder is for phosphorus aluminium glue and/or containing the first clay
Phosphorus aluminium inorganic binder, on the basis of the phosphorus aluminium inorganic binder butt weight for containing the first clay, described is viscous containing first
The phosphorus aluminium inorganic binder of soil is included with Al2O3Count 15-40 weight % aluminium component (the aluminium component does not come from the first clay), with
P2O5Count 45-80 weight % phosphorus component and 0 and the first clay no more than 40 weight %, and its are more than with dry basis
P/Al weight ratio is 1.0-6.0, and pH value 1-3.5, solid content is 15-60 weight %；N (the SiO of the molecular sieve2)/n
(Al2O3) it is more than 100；With P2O5Count and on the basis of the butt weight of molecular sieve, the phosphorus content of the molecular sieve is 0.1-5
Weight %；The Al distributed constants D of the molecular sieve meets：0.5≤D≤0.8, wherein, D=Al (S)/Al (C), Al (S) represent to adopt
The inside H in crystal face edge of the zeolite crystal determined with TEM-EDS methods is apart from interior any aluminium for being more than 100 square nanometers regions
Content, Al (C) represent to appoint in the outside H distances of geometric center using crystal face described in the zeolite crystal of TEM-EDS methods measure
Meaning is more than the aluminium content in 100 square nanometers regions, wherein the H, which is the crystal face edge point, arrives the crystal face geometric center distance
10%；The ratio that the mesopore volume of the molecular sieve accounts for total pore volume is 15-30 bodies %；The strong acid acid amount of the molecular sieve accounts for
The ratio of total acid content is 60-80%, and the ratio between B acid acid amounts and L acid acid amounts are 20-100.
Preferably, the molecular sieve n (SiO2)/n(Al2O3) it is more than 120；With P2O5Count and using the butt weight of molecular sieve as
Benchmark, the phosphorus content of the molecular sieve is 0.1-4 weights %；The Al distributed constants D of the molecular sieve meets：0.55≤D≤0.75；
The ratio that the mesopore volume of the molecular sieve accounts for total pore volume is 20-25 bodies %；The strong acid acid amount of the molecular sieve accounts for total acid content
Ratio be 70-75%, the ratio between B acid acid amounts and L acid acid amounts are 30-80.
Preferably, the first described clay is selected from kaolin, sepiolite, concave convex rod, rectorite, montmorillonite and diatomite
At least one of；Second clay is selected from kaolin, metakaolin, diatomite, sepiolite, attapulgite, montmorillonite
At least one of with rectorite；Described other inorganic matter binding agents are selected from boehmite, Alumina gel, silicon-aluminum sol and water
At least one of glass.
Preferably, the metallic addition introduces the auxiliary agent in the form of metallic compound, and the metallic compound is
Selected from least one of oxide, hydroxide, chloride, nitrate, sulfate, phosphate and organic compound.
Preferably, on the basis of the butt weight of the auxiliary agent, the auxiliary agent also contains with P2O5Meter is no more than 5 weight %
Phosphorus additive.
Preferably, the auxiliary agent includes 8-25 weight % phosphorus aluminium inorganic binder, 20-60 weight % phosphorous MFI knots
Structure molecular sieve, 10-45 weight % the second clay, 5-25 weight % other inorganic binders, 1.0-10 weight % metal
The phosphorus additive of additive and 0-3 weight %.
The present invention also provides a kind of preparation method for the assistant for calalytic cracking for improving octane number bucket, and this method includes：
Phosphorous MFI structure molecular sieve, phosphorus aluminium inorganic binder and other inorganic binders are mixed, adds or is added without the second clay, beat
Slurry, spray drying；Wherein, metallic addition is introduced, introduces or does not introduce phosphorus additive；With total butt of the preparing raw material of auxiliary agent
On the basis of weight, the preparing raw material of the auxiliary agent is included with dry basis 10-75 weight % phosphorous MFI structure molecular sieve,
With dry basis 3-40 weight % phosphorus aluminium inorganic binder, the weight of the 1-30 in terms of oxide % other inorganic binders,
With dry basis 0-60 weight % the second clay, the weight of the 0.5-15 in terms of oxide % selected from VIII race's metal and manganese, zinc,
The metallic addition of at least one of gallium, and including or not include with P2O5Phosphorus additive of the meter no more than 5 weight %；Its
In, described phosphorus aluminium inorganic binder is phosphorus aluminium glue and/or the phosphorus aluminium inorganic binder containing the first clay, and to contain first viscous with described
On the basis of the phosphorus aluminium inorganic binder butt weight of soil, the phosphorus aluminium inorganic binder for containing the first clay is included with Al2O3Meter
15-40 weight % aluminium component, with P2O5Count 45-80 weight % phosphorus component and be more than 0 with dry basis and be no more than 40 weights
% the first clay is measured, and its P/Al weight ratio is 1.0-6.0, pH value 1-3.5, solid content is 15-60 weight %；Described point
N (the SiO of son sieve2)/n(Al2O3) it is more than 100；With P2O5Count and on the basis of the butt weight of molecular sieve, the phosphorus of the molecular sieve
Content is 0.1-5 weights %；The Al distributed constants D of the molecular sieve meets：0.5≤D≤0.8, wherein, D=Al (S)/Al (C),
Al (S) represents the inside H in crystal face edge using the zeolite crystal of TEM-EDS methods measure apart from interior any more than 100 squares
The aluminium content of nano-area, Al (C) represent using TEM-EDS methods measure zeolite crystal described in crystal face geometric center to
Outer H is apart from interior any aluminium content for being more than 100 square nanometers regions, wherein the H, which is the crystal face edge point, arrives the crystal face
The 10% of geometric center distance；The ratio that the mesopore volume of the molecular sieve accounts for total pore volume is 15-30 bodies %；The molecular sieve
Strong acid acid amount to account for the ratio of total acid content be 60-80%, it is 20-100 that the ratio between B acid acid amounts and L acid acid, which are measured,.
Preferably, the preparation process of the phosphorous MFI structure molecular sieve includes：A, sodium form MFI structure molecular sieve is carried out
Ammonium exchanges, and obtains ammonium and exchanges molecular sieve；Wherein, on the basis of total butt weight that sodium oxide molybdena is counted and exchanges molecular sieve by ammonium, institute
The sodium content for stating ammonium exchange molecular sieve is less than 0.2 heavy %；B, gained ammonium in step a is exchanged into molecular sieve by fluosilicic acid, organic
Dealumination treatment is carried out in the Compound-acid dealuminzation agent solution of acid and inorganic acid composition, and after being filtered and being washed, obtains dealuminzation point
Son sieve；C, after the dealuminzation molecular sieve of gained in step b being carried out into P Modification processing and calcination process, the phosphorous MFI knots are obtained
Structure molecular sieve.
Preferably, also include the step of dealumination treatment described in step b：Organic acid first is exchanged into molecular sieve with the ammonium to mix
Close, then fluosilicic acid and inorganic acid are exchanged to molecular sieve mixing with the ammonium.
Preferably, the condition of dealumination treatment is described in step b：With the molecular sieve, fluosilicic acid, organic acid of dry basis
Weight ratio with inorganic acid is 1：(0.02-0.5):(0.05-0.5):(0.05-0.5)；Treatment temperature is 25-100 DEG C, place
The reason time is 0.5-6 hours；Organic acid described in step b is selected from ethylenediamine tetra-acetic acid, oxalic acid, citric acid and sulfosalicylic acid
At least one of, inorganic acid is selected from least one of hydrochloric acid, sulfuric acid and nitric acid.
Preferably, the processing of P Modification described in step c includes：Phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and phosphoric acid will be selected from
Molecular sieve is impregnated at least one of ammonium phosphorus-containing compound and/or ion exchange；The condition of the calcination process includes：
The atmosphere of calcination process is air atmosphere or steam atmosphere；Sintering temperature is 400-800 DEG C, and roasting time is 0.5-8 hours.
Preferably, the preparation process of the phosphorus aluminium inorganic binder for containing the first clay includes：(1), by alumina source,
One clay is dispersed into the slurries that solid content is 8-45 weight % with water mashing；Described alumina source is can be by the hydrogen-oxygen of sour peptization
Change aluminium and/or aluminum oxide, with the first clay of dry basis and with Al2O3The weight ratio of the alumina source of meter is (to be more than 0-
40):(15-40)；(2), concentrated phosphoric acid is added according to P/Al=1-6 part by weight in the lower slurries obtained toward step (1) of stirring；
(3) slurries that step (2) obtains, are reacted into 15-90 minutes at a temperature of 50-99 DEG C.The phosphorus aluminium glue is existing catalytic cracking
One or more in the phosphorus Alumina gel and/or phosphorus alumina gel that are used in catalyst preparation.Described phosphorus aluminium glue for example can be by
Following method is prepared：Silicon source and water are mixed with beating to obtain slurries, then phosphorus source is added in the slurries, in 40-
0.1-10h is contacted at 100 DEG C and obtains the phosphorus aluminium glue that pH value is 1.0-3.5.A kind of embodiment, the phosphorus aluminium glue preparation method is such as
Under：By the molten aluminum oxide of theobromine or the aluminium hydroxide scattered mashing of deionized water, the solid content 20-40wt%, Ran Housheng of slurries
Temperature is (0.30-1.0) by Al/P atomic ratios to 95-110 DEG C:1 ratio, phosphoric acid is added, and keep reacting 0.5-2 hours, directly
To transparent colloid is become, phosphorus aluminium glue is made.Another embodiment, the P/Al weight ratio of the phosphorus aluminium glue is 1.0-6.0, pH
It is 15-45 weight % to be worth for 1-3.5, solid content, and preferably 20-40% weight, surplus are water.
Assistant for calalytic cracking provided by the invention, there is preferable Catalytic Cracking Performance, urged after being blended with host for heavy oil
Change cracking reaction, catalytically cracked gasoline octane number bucket can be improved, while alkene and aromatic hydrocarbon concentration is not increased, significantly carried
The content of isohydrocarbon in high gasoline, and then improve octane number.For example, industrial poising agent DVR-3 is in 500 DEG C, weight (hourly) space velocity (WHSV)
For 8h-1, oil ratio reacted under conditions of being 6, the weight % of liquefied gas 14.62, heavy oil yield is 15.07 weight %, gasoline
Yield is 43.73 weight %, and isomery hydrocarbon content is 24.76 weight % in gasoline, and olefin(e) centent is 28.27 weight %, aromatic hydrocarbon
Content is 35.83 weight %, octane number 88.9, octane number bucket 38.88.It is and provided by the invention including the phosphorous of 50 weight %
MFI structure molecular sieve, 18 weight % kaolin, 20 weight % phosphorus aluminium inorganic binders, 3 weight % boehmites, 7 weight %
The metallic addition of the auxiliary agent of Alumina gel and 2 weight %, with 10：After 90 weight ratio mixes with above-mentioned poising agent DVR-3, same
Reacted under the conditions of sample, the weight % of liquefied gas 14.18, heavy oil yield is 16.32 weight %, and gasoline yield is 43.15 weights
% is measured, isomery hydrocarbon content is 27.03 weight % in gasoline, and olefin(e) centent is 25.72 weight %, and aromatic hydrocarbon content is 36.28 weights
Measure %, octane number 91.7, octane number bucket 39.57.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
To achieve these goals, the present invention provides a kind of assistant for calalytic cracking for improving octane number bucket, with described
On the basis of the butt weight of auxiliary agent, the auxiliary agent is included with dry basis 10-75 weight % phosphorous MFI structure molecular sieve, with
Dry basis 3-40 weight % phosphorus aluminium inorganic binder, the weight of the 1-30 in terms of oxide % other inorganic binders, with
Dry basis 0-60 weight % the second clay, and the weight of the 0.5-15 in terms of oxide % selected from VIII race's metal and manganese, zinc,
The metallic addition of at least one of gallium；Wherein, described phosphorus aluminium inorganic binder is for phosphorus aluminium glue and/or containing the first clay
Phosphorus aluminium inorganic binder, it is described to contain the first clay on the basis of the phosphorus aluminium inorganic binder butt weight for containing the first clay
Phosphorus aluminium inorganic binder include with Al2O3Count 15-40 weight % aluminium component (the aluminium component does not come from the first clay), with
P2O5Count 45-80 weight % phosphorus component and 0 and the first clay no more than 40 weight %, and its are more than with dry basis
P/Al weight ratio is 1.0-6.0, and pH value 1-3.5, solid content is 15-60 weight %；N (the SiO of the molecular sieve2)/n
(Al2O3) it is more than 100, preferably greater than more than 120；With P2O5Count and on the basis of the butt weight of molecular sieve, the molecular sieve
Phosphorus content is 0.1-5 weight %, preferably 0.1-4 weights %；The Al distributed constants D of the molecular sieve meets：0.5≤D≤0.8, it is excellent
Be full foot：0.55≤D≤0.75, wherein, D=Al (S)/Al (C), Al (S) represent the molecular sieve using TEM-EDS methods measure
The inside H in crystal face edge of crystal grain represents to use TEM-EDS apart from interior any aluminium content for being more than 100 square nanometers regions, Al (C)
The outside H of geometric center of crystal face described in the zeolite crystal of method measure is apart from interior any aluminium for being more than 100 square nanometers regions
Content, wherein the H, which is the crystal face edge point, arrives the 10% of the crystal face geometric center distance；The middle hole body of the molecular sieve
The ratio that product accounts for total pore volume is 15-30 body %, preferably 20-25 bodies %；The strong acid acid amount of the molecular sieve accounts for total acid content
Ratio is 60-80%, preferably 70-75%, and the ratio between B acid acid amounts and L acid acid amounts are 20-100, preferably 30-80.
According to the present invention, the phosphorus aluminium inorganic binder is phosphorus aluminium inorganic binder and/or phosphorus aluminium glue containing the first clay.
A kind of embodiment, on the basis of the butt weight of the phosphorus aluminium inorganic binder, described phosphorus aluminium is inorganic
Binding agent is included with Al2O3Count 15-40 weight % aluminium component, with P2O5Count 45-80 weight % phosphorus component and with butt weight
0-40 weight % the first clay is counted, and its P/Al weight ratio is 1.0-6.0, pH value 1-3.5, solid content is 15-60 weights
Measure %；Such as including with Al2O3Count 15-40 weight % aluminium component, with P2O5Count 45-80 weight % phosphorus component and with butt
Weight meter 1-40 weight % the first clay；Preferably comprise with Al2O315-35 weight % aluminium component is counted, with P2O5Count 50-75
Weight % phosphorus component and the first clay with dry basis 8-35 weight %, its P/Al weight than preferably 1.2-6.0,
More preferably 2.0-5.0, pH value are preferably 1.5-3.0.
Another embodiment, on the basis of the butt weight of the phosphorus aluminium inorganic binder, described phosphorus aluminium without
Machine binding agent is included with Al2O3Count 20-40 weight % aluminium component and with P2O5Count 60-80 weight % phosphorus component.
According to the molecular sieve of the present invention, the aluminium content that molecular sieve is determined using TEM-EDS methods is those skilled in the art
Known, wherein the geometric center is also well-known to those skilled in the art, can be calculated according to formula, this hair
Bright to repeat no more, the geometric center of generally symmetrical figure is the intersection point of each opposed apexes line, for example, conventional six square shape sheet ZSM-
Point of intersection of the geometric center of 5 hexagon crystal face in three opposed apexes.
According to the molecular sieve of the present invention, well-known to those skilled in the art to be, the mesopore volume of the molecular sieve accounts for always
The ratio of pore volume can be measured using N2 adsorption BET specific surface area method, and the mesopore volume is that aperture is more than 2 nanometers
Pore volume less than 100 nanometers；The ratio that the strong acid acid amount of the molecular sieve accounts for total acid content can use NH3- TPD methods are carried out
Measurement, the acid site of the strong acid is NH3Desorption temperature is more than the acid site corresponding to 300 DEG C；The B acid acid amount and L acid acid
The ratio between amount can be measured using the infrared acid process of pyridine adsorption.
According to the present invention, metallic addition adds in pulping process, and it can be the gold in the auxiliary agent for preparing shaping
The form for belonging to compound introduces, and for example, selected from oxide, hydroxide, chloride, nitrate, sulfate, phosphate and has
In at least one of machine compound, preferably autoxidisable substance, orthophosphates, phosphite, subphosphate and acid phosphate
One or more forms introduce or exist.
According to the present invention, clay is well known to those skilled in the art, the first described clay can be selected from kaolin,
At least one of sepiolite, concave convex rod, rectorite, montmorillonite and diatomite, rectorite is preferably included, more preferably tired support
Soil；Second clay can be selected from kaolin, metakaolin, sepiolite, attapulgite, montmorillonite, rectorite, diatom
At least one of soil, galapectite, saponite, boron-moisten soil and hydrotalcite, it preferably is selected from kaolin, metakaolin, diatomite, Hai Pao
At least one of stone, attapulgite, montmorillonite and rectorite；Other inorganic binders can be selected from except the phosphorus aluminium glue
With the inorganic oxide binder for being customarily used in assistant for calalytic cracking or catalyst binder component beyond phosphorus aluminium inorganic binder
In one or more, preferably be selected from least one of boehmite, Alumina gel, silicon-aluminum sol and waterglass, more preferably from
At least one of boehmite and Alumina gel.
According to the present invention, the phosphorus aluminium inorganic binder for containing the first clay is preferably comprised with Al2O3Count 15-35 weight %
Aluminium component, with P2O5Count 50-75 weight % phosphorus component and the first clay with dry basis 8-35 weight %, its P/
For Al weight than preferably 2.0-5.0, preferably 1.2-6.0, more preferably 2.0-5.0, pH value is preferably 1.0-3.5.
According to the present invention, on the basis of the butt weight of the auxiliary agent, the auxiliary agent can also contain with P2O5Meter is no more than
5 weight % phosphorus additive.Described phosphorus additive can be selected from the compound of phosphorus, such as the inorganic compound including phosphorus and have
One or more in machine compound can be soluble in water or be insoluble in water or phosphorus compound not soluble in water,
Be selected from the oxide of phosphorus, phosphoric acid, orthophosphates, phosphite, hypophosphites, subphosphate, acid phosphate and
One or more in phosphorous organic compound.Preferable phosphorus compound is phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate, phosphoric acid hydrogen
One or more in two ammoniums and aluminum phosphate.In resulting auxiliary agent, phosphorus additive is with the phosphorus compound (oxide of such as phosphorus, just
Phosphate, phosphite, subphosphate and acid phosphate) form exist.The phosphorus additive may reside in auxiliary agent
Any position that may be present, it such as may reside in inside the duct of zeolite, the surface of zeolite, may reside in host material
In (material i.e. in auxiliary agent in addition to molecular sieve), it can also be present in simultaneously inside the duct of zeolite, the surface of zeolite and institute
State in host material.Do not include the phosphorus in molecular sieve in the content of phosphorus additive, do not draw including the phosphorus aluminium inorganic binder yet
The phosphorus entered.
According to the present invention, the auxiliary agent preferably includes 8-25 weight % phosphorus aluminium inorganic binder, 20-60 weight % contains
Phosphorus MFI structure molecular sieve, 10-45 weight % the second clay, 5-25 weight % other inorganic binders, 1.0-10 weight %
Metallic addition and 0-3 weight % phosphorus additive.
The present invention also provides a kind of preparation method for the assistant for calalytic cracking for improving octane number bucket, and this method includes：
Phosphorous MFI structure molecular sieve, phosphorus aluminium inorganic binder and other inorganic binders are mixed, adds or is added without the second clay, beat
Slurry, spray drying；Wherein, metallic addition is introduced, introduces or does not introduce phosphorus additive；With total butt of the preparing raw material of auxiliary agent
On the basis of weight, the preparing raw material of the auxiliary agent is included with dry basis 10-75 weight % phosphorous MFI structure molecular sieve,
With dry basis 3-40 weight % phosphorus aluminium inorganic binder, the weight of the 1-30 in terms of oxide % other inorganic binders,
With dry basis 0-60 weight % the second clay, the weight of the 0.5-15 in terms of oxide % selected from VIII race's metal and manganese, zinc,
The metallic addition of at least one of gallium, and including or not include with P2O5Phosphorus additive of the meter no more than 5 weight %；Its
In, described phosphorus aluminium inorganic binder is phosphorus aluminium glue and/or the phosphorus aluminium inorganic binder containing the first clay, and to contain first viscous with described
On the basis of the phosphorus aluminium inorganic binder butt weight of soil, the phosphorus aluminium inorganic binder for containing the first clay is included with Al2O3Meter
15-40 weight % aluminium component, with P2O5Count 45-80 weight % phosphorus component and be more than 0 with dry basis and be no more than 40 weights
% the first clay is measured, and its P/Al weight ratio is 1.0-6.0, pH value 1-3.5, solid content is 15-60 weight %；Described point
N (the SiO of son sieve2)/n(Al2O3) it is more than 100；With P2O5Count and on the basis of the butt weight of molecular sieve, the phosphorus of the molecular sieve
Content is 0.1-5 weights %；The Al distributed constants D of the molecular sieve meets：0.5≤D≤0.8, wherein, D=Al (S)/Al (C),
Al (S) represents the inside H in crystal face edge using the zeolite crystal of TEM-EDS methods measure apart from interior any more than 100 squares
The aluminium content of nano-area, Al (C) represent using TEM-EDS methods measure zeolite crystal described in crystal face geometric center to
Outer H is apart from interior any aluminium content for being more than 100 square nanometers regions, wherein the H, which is the crystal face edge point, arrives the crystal face
The 10% of geometric center distance；The ratio that the mesopore volume of the molecular sieve accounts for total pore volume is 15-30 bodies %；The molecular sieve
Strong acid acid amount to account for the ratio of total acid content be 60-80%, it is 20-100 that the ratio between B acid acid amounts and L acid acid, which are measured,.Those skilled in the art
It is well known that the solid content for the slurries being spray-dried can be 10-50%.
According to the present invention, the preparation process of the phosphorous MFI structure molecular sieve can include：A, by sodium form MFI structure point
Son sieve carries out ammonium exchange, obtains ammonium and exchanges molecular sieve；Wherein, in terms of sodium oxide molybdena and using ammonium exchange molecular sieve total butt weight as
Benchmark, the sodium content that the ammonium exchanges molecular sieve are less than 0.2 heavy %；B, gained ammonium in step a is exchanged into molecular sieve by fluorine silicon
Dealumination treatment is carried out in the Compound-acid dealuminzation agent solution of acid, organic acid and inorganic acid composition, and after being filtered and being washed, is obtained
Dealuminzation molecular sieve；C, after the dealuminzation molecular sieve of gained in step b being carried out into P Modification processing and calcination process, obtain described phosphorous
MFI structure molecular sieve.
According to the present invention, the sodium form MFI structure molecular sieve be it is well-known to those skilled in the art, can be by non-amine method
, can also be by gained after the molecular sieve roasting of template agent method preparation obtained by crystallization, for example, ZSM-5 molecular sieve, silica alumina ratio can be with small
In 100.
According to the present invention, it is well-known to those skilled in the art that the ammonium, which exchanges, for example, can be by sodium form MFI structure
Molecular sieve is according to molecular sieve：Ammonium salt：H2O=1：(0.1-1)：The weight ratio of (5-10) is small to exchange 0.5-2 at 100 DEG C in room temperature
When after filter, this exchange process repeat 1-4 times, make the Na on zeolite2O content is less than 0.2 heavy %.Described ammonium salt can be normal
Inorganic ammonium salt, for example, selected from least one of ammonium chloride, ammonium sulfate and ammonium nitrate.
According to the present invention, the dealumination treatment of molecular sieve is well-known to those skilled in the art, but do not reported will be inorganic
Acid, organic acid and fluosilicic acid are used for dealumination treatment together.The dealumination treatment can be carried out once or several times, will first can be had
Machine is sour to exchange molecular sieve mixing with the ammonium, then fluosilicic acid and inorganic acid are exchanged to molecular sieve mixing with the ammonium, you can with
Exchanged for organic acid first is added into ammonium in molecular sieve, then by fluosilicic acid and inorganic acid, cocurrent adds at a slow speed, or first adds fluorine silicon
Acid adds inorganic acid, and preferably cocurrent adds at a slow speed for fluosilicic acid and inorganic acid.
According to the present invention, the condition of dealumination treatment can be described in step b：With the molecular sieve of dry basis, fluorine silicon
The weight ratio of acid, organic acid and inorganic acid is 1：(0.02-0.5):(0.05-0.5):(0.05-0.5), preferably 1：
(0.05-0.3):(0.1-0.3):(0.1-0.3), if fluosilicic acid, organic acid and/or inorganic acid are solution, the weight ratio
In terms of the solute of fluosilicic acid, organic acid and inorganic acid, the not solvent including dissolving acid；Treatment temperature is 25-100 DEG C, during processing
Between be 0.5-6 hours；Organic acid and inorganic acid are well known to the skilled person, for example, organic acid can described in step b
Think that, selected from least one of ethylenediamine tetra-acetic acid, oxalic acid, citric acid and sulfosalicylic acid, inorganic acid can be selected from salt
At least one of acid, sulfuric acid and nitric acid.
According to the present invention, washing is well-known to those skilled in the art, and its mode can be：By 5-10 times 30-60 DEG C
Water molecular sieve after filtering is eluted.
According to the present invention, P Modification processing and roasting are well known to those skilled in the art, described in step c at P Modification
Reason can include：At least one of phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate phosphorus-containing compound will be selected to molecule
Sieve is impregnated and/or ion exchange；The condition of the calcination process can include：The atmosphere of calcination process be air atmosphere or
Steam atmosphere；Sintering temperature is 400-800 DEG C, and roasting time is 0.5-8 hours.
According to the present invention, the preparation process of the phosphorus aluminium inorganic binder for containing the first clay can include：(1), by oxygen
Change silicon source, the first clay and water mashing and be dispersed into the slurries that solid content is 8-45 weight %；Described alumina source is can be sour
The aluminium hydroxide and/or aluminum oxide of peptization, with the first clay of dry basis and with Al2O3The weight ratio of the alumina source of meter
For (being more than 0-40):(15-40)；(2), add in the lower slurries obtained toward step (1) of stirring according to P/Al=1-6 part by weight
Enter concentrated phosphoric acid；In wherein described P/Al P be phosphoric acid in the phosphorus in terms of simple substance weight, Al be alumina source in terms of simple substance
Aluminium weight；(3) slurries that step (2) obtains, are reacted into 15-90 minutes at a temperature of 50-99 DEG C.
According to the present invention, the alumina source can be selected from ρ-aluminum oxide, χ-aluminum oxide, η-aluminum oxide, gamma oxidation
Aluminium, κ-aluminum oxide, δ-aluminum oxide, θ-aluminum oxide, gibbsite, surge aluminium stone, promise diaspore, diaspore, boehmite and plan
At least one of boehmite, the aluminium component in the phosphorus aluminium inorganic binder for containing the first clay are derived from described aluminum oxide
Source.The first described clay can be kaolin, sepiolite, concave convex rod, rectorite, montmorillonite and diatomite in one kind or
It is a variety of, preferably rectorite.Its concentration of described concentrated phosphoric acid can be 60-98 weight %, more preferably 75-90 weight %.Phosphorus
Acid charging rate be preferably 0.01-0.10Kg phosphoric acid/minute/Kg alumina sources, more preferably 0.03-0.07Kg phosphoric acid/point
Clock/Kg alumina sources.
According to the present invention, the phosphorus aluminium inorganic binder for containing the first clay was not only being prepared due to the introducing of clay
Mass transfer, the heat transfer of storeroom are improved in journey, avoids and is glued caused by the uneven local moment vigorous reaction heat release overtemperature of material
Agent solidification is tied, the adhesive property of obtained binding agent is suitable with the phosphorus al binder for not introducing clay mitigation preparation；And the party
Method introduces clay, the especially rectorite with layer structure, improves the heavy oil conversion performance of carbon monoxide-olefin polymeric, so as to get
Auxiliary agent have it is more preferably selective.
The preparation method of assistant for calalytic cracking provided by the invention, by phosphorous MFI structure molecular sieve, phosphorus aluminium inorganic binder
Mixed with other inorganic binders, mashing, its order to feed does not have a particular/special requirement, such as can by phosphorus aluminium inorganic binder,
Other inorganic binders, molecular sieve, the mixing of the second clay (can then omit the charging step of correlation when without the second clay
Suddenly it is beaten), it is preferred that the phosphorus aluminium is added after being first mixed with beating the second clay, molecular sieve and other inorganic binders
Inorganic binder, this is advantageous to the activity and selectivity for improving auxiliary agent.
Assistant for calalytic cracking preparation method provided by the invention, in addition to the slurries spray drying that the mashing is obtained
Step.The method of spray drying is known to those skilled in the art, the present invention does not have particular/special requirement.
In the preparation method of assistant for calalytic cracking provided by the present invention, it can be introduced by introducing the form of metallic compound
Described metallic addition, metallic addition can be in any steps before the spray drying forming of auxiliary agent preparation process toward slurry
Metallic compound is added in liquid and is introduced；Dipping or chemisorbed metallic can also be passed through after auxiliary agent spray drying forming
Be calcined and introduce after compound, including by auxiliary agent impregnated with the metal-containing compound aqueous solution or chemisorbed handle, Ran Houjin
Row separation of solid and liquid (if desired), dry and be calcined, wherein dry temperature can be room temperature to 400 DEG C, preferably 100-
300 DEG C, the temperature of roasting can be 400-700 DEG C, and preferably 450-650 DEG C, roasting time can be 0.5-100 hours, excellent
Elect 0.5-10 hours as.The one kind or more of described metallic compound in their inorganic compound and organic compound
Kind, it can be soluble in water or be insoluble in water or compound not soluble in water.The example of metallic compound includes gold
The oxide of category, hydroxide, chloride, nitrate, sulfate, phosphate, the organic compound etc. of metal.Preferable metal
One or more of the compound in their chloride, nitrate, sulfate and phosphate.
In assistant for calalytic cracking provided by the present invention, the metallic addition may reside in that auxiliary agent is any to be there may be
Position, such as may reside in inside the duct of zeolite, the surface of zeolite, may reside in host material, can also be simultaneously
It is present in inside the duct of zeolite, in the surface of zeolite and the host material, is preferably in host material.Described gold
Category additive can exist in the form of their oxide, orthophosphates, phosphite, subphosphate and acid phosphate etc..
Assistant for calalytic cracking preparation method provided by the present invention, when containing phosphorus additive in auxiliary agent, described phosphorus adds
Add agent that the combination of one of following method or several method can be used to introduce, but be not limited to these methods and introduce auxiliary agent
In：
1st, phosphorus compound is added in slurries in going to for auxiliary agent spray drying forming；
2nd, after auxiliary agent spray drying forming through dipping or chemisorbed phosphorus compound, through separation of solid and liquid (if desired
If), dry and roasting process introduces, the temperature of the drying can be room temperature to 400 DEG C, preferably 100-300 DEG C, roasting
Temperature can be 400-700 DEG C, and preferably 450-650 DEG C, roasting time can be 0.5-100 hours, and preferably 0.5-10 is small
When.The phosphorus compound can be selected from the one or more in the various inorganic compounds and organic compound of phosphorus.The phosphatization
Compound can be soluble in water or be insoluble in water or phosphorus compound not soluble in water.The embodiment bag of phosphorus compound
Include the oxide of phosphorus, phosphoric acid, orthophosphates, phosphite, hypophosphites, phosphorous organic compound etc..Preferable phosphatization is closed
One or more of the thing in phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate and aluminum phosphate.
Thus, the phosphorus additive may reside in any position that may be present of auxiliary agent, as may reside in zeolite
Inside duct, the surface of zeolite, may reside in the host material, can also be present in simultaneously inside the duct of zeolite,
In the surface of zeolite and the host material.The phosphorus additive is with phosphorus compound (oxide of such as phosphorus, orthophosphates, phosphorous
Hydrochlorate, subphosphate, acid phosphate) form exist.
Assistant for calalytic cracking provided by the invention is applied to various hydrocarbon oil catalytic crackings., can during for catalytic cracking process
Individually toward adding in catalyst cracker, used after can also being mixed with catalytic cracking catalyst.Generally, the present invention carries
The auxiliary agent of confession accounts for FCC catalyst and is no more than 30 weight %, preferably 1-25 weights with agent mixture total amount provided by the invention
%, more preferably 3-15 weight % are measured, the hydrocarbon ils be selected from various petroleum distillates, such as crude oil, reduced crude, decompression residuum, normal
Press wax oil, decompressed wax oil, straight-run gas oil, propane it is light/one or more in de-oiling, wax tailings and coal liquefaction products again.Institute
Beavy metal impurity and sulphur, the nitrogen impurities such as nickel, vanadium can be contained by stating hydrocarbon ils, as the content of sulphur may be up to 3.0 weight %, the content of nitrogen
The content of the metal impurities such as up to 2.0 weight %, vanadium, nickel may be up to 3000ppm.
Assistant for calalytic cracking provided by the invention is used in catalytic cracking process, and hydrocarbon oil catalytic cracking condition is urged for conventional
Change cracking conditions.In general, it is 400-600 DEG C that the hydrocarbon oil catalytic cracking condition, which includes reaction temperature, preferably 450-550
DEG C, weight (hourly) space velocity (WHSV) is 8-120 hours-1, preferably 8-80 hours-1, oil ratio (weight ratio) is 1-20, preferably 3-15.This hair
The assistant for calalytic cracking of bright offer can be used for existing various catalyst crackers, such as anti-in fixed bed reactors, fluid bed
Answer and carried out in device, riser reactor, multi-reaction-area reactor etc..
The present invention will be further illustrated by embodiment below, but the present invention is not therefore subject to any restriction,
Instrument and reagent used by the embodiment of the present invention, unless otherwise instructed, be the instrument commonly used of those skilled in the art and
Reagent.
The crystallinity of the present invention is measured using ASTM D5758-2001 (2011) e1 standard method.
N (the SiO of the present invention2)/n(Al2O3), i.e., silica alumina ratio is obtained by the cubage of silica and aluminum oxide, oxidation
The content of silicon and aluminum oxide is measured using GB/T 30905-2014 standard methods.
The phosphorus content of the present invention is measured using GB/T 30905-2014 standard methods.
The TEM-EDS assay methods of the present invention are referring to the research method of solid catalyst, petrochemical industry, 29 (3), and 2000：
227。
The ratio surface of the present invention is measured using GB5816 standard methods.
The pore volume of the present invention is measured using GB5816 standard methods.
The strong acid acid amount and total acid content of the present invention uses NH3- TPD methods are measured, referring to the research of solid catalyst
Method, petrochemical industry, 30 (12), 2001：952.
The B acid acid amounts of the present invention are measured with L acid acid amounts using Pyridine adsorption IR spectra method, referring to solid catalyst
Research method, petrochemical industry, 29 (8), 2000：621.
The sodium content of the present invention is measured using GB/T 30905-2014 standard methods.
The computational methods of D values are as follows：A crystal grain is chosen in transmission electron microscope and some crystal face of the crystal grain is formed
One polygon, the 10% distance H that the polygon has geometric center, edge and geometric center to edge point are (different
Edge point, H values are different), choose respectively any one piece in the inside H distances in the crystal face edge be more than 100 square nanometers regions with
And any one piece in the outside H distances of crystal face geometric center is more than 100 square nanometers regions, determines aluminium content, as Al (S1)
With Al (C1), and D1=Al (S1)/Al (C1) is calculated, choose different crystal grain respectively and determine 5 times, it is D to calculate average value.
Reaction product of the present invention is by N2Bring -10 DEG C of liquid into and receive in bottle and carry out gas-liquid separation, gaseous product collect complete by
The GC of Agilent 6890 (TCD detectors) on-line analysis forms；Weighed off line after liquid product collection, simulation steaming is carried out respectively
Evaporate and analyze (being tested using RIPP81-90 method of testings) with gasoline detailed hydrocarbon, the cut cut point difference of gasoline and diesel oil
For 221 DEG C and 343 DEG C；Green coke catalyst carries out coke and sulfur content point after drawing off on the carbon and sulfur analytical instruments of multi EA 2000
Analyse (being tested using RIPP106-90 method of testings), all product qualities add and calculated material balance, and octane number uses
RIPP 85-90 methods are determined, and gasoline PONA compositions are determined using gasoline detailed hydrocarbon analysis, and octane number bucket=octane number (RON) ×
Yield of gasoline.
RIPP standard methods of the present invention for details, reference can be made to《Petrochemical Engineering Analysis method》, Yang Cui surely compile by grade, and 1990
Year version.
Part material property used is as follows in embodiment：
Boehmite is that Shandong Aluminium Industrial Corp produces industrial products, the weight % of solid content 60；Alumina gel is urged for sinopec
The industrial products of agent asphalt in Shenli Refinery production, Al2O3Content is 21.5 weight %；Ludox is sinopec catalyst Shandong point
The industrial products of company's production, SiO2Content is 28.9 weight %, Na2O content 8.9%；Kaolin is given birth to for Kaolin of Suzhou company
The special kaolin of catalytic cracking catalyst of production, solid content are 78 weight %.Concentration of hydrochloric acid is 36 weight %, and rectorite is Hubei
Distinguished personages' rectorite development corporation, Ltd. of Zhongxiang City product, quartz sand content<3.5 weight %, Al2O3Content is 39.0 weight %,
Fe2O3Content is 2.0 weight %, Na2O content is 0.03 weight %, and solid content is 77 weight %；SB aluminium hydrate powders：Germany
Condex companies produce, Al2O3Content is 75 weight %；Gamma oxidation aluminium powder：German Condex companies production, Al2O3Content is
95 weight %.Hydrochloric acid：Chemistry is pure, and concentration is 36-38 weight %, and Beijing Chemical Plant produces.
Embodiment 1-3 provides the phosphorous MFI structure molecular sieve of the present invention.
Embodiment 1
By ZSM-5 molecular sieve, (catalyst asphalt in Shenli Refinery produces, non-amine method synthesis, n (SiO2)/n(Al2O3)=27) use
NH4Cl solution exchanges washing to Na2O content is less than 0.2 weight %, filters to obtain filter cake；Take above-mentioned molecular sieve 100g (butt) plus water
The weight of solid content 10 % molecular sieve pulp is configured to, oxalic acid 20g is added in stirring, then by 200g hydrochloric acid (mass fraction 10%)
Added with 167g fluosilicic acid (mass fraction 3%) cocurrent, add time 30min；It is warming up to 65 DEG C of constant temperature stirring 1h, filtering washing
It is neutral to filtrate；By filter cake plus water be beaten solid content be 40 weight % molecular sieve pulps, add 2.4gH3PO4(the weight of concentration 85
Measure %), be uniformly mixed with dipping, drying, 550 DEG C of calcination process 2 hours.Molecular sieve-4 A is obtained, physico-chemical property data are listed in table 1.
Comparative example 1
By ZSM-5 molecular sieve, (catalyst asphalt in Shenli Refinery produces, non-amine method synthesis, n (SiO2)/n(Al2O3)=27) use
NH4Cl solution exchanges washing to Na2O content is less than 0.2 weight %, filters to obtain filter cake；Take above-mentioned molecular sieve 100g (butt) plus water
The weight of solid content 10 % molecular sieve pulp is configured to, oxalic acid 48g is added in stirring；It is warming up to 65 DEG C of constant temperature stirring 1h, filter water
It is washed till filtrate neutrality；By filter cake plus water be beaten solid content be 40 weight % molecular sieve pulps, add 2.4gH3PO4(the weight of concentration 85
Measure %), be uniformly mixed with dipping, drying, 550 DEG C of calcination process 2 hours.Molecular sieve DA1 is obtained, physico-chemical property data are listed in table 1.
Comparative example 2
By ZSM-5 molecular sieve, (catalyst asphalt in Shenli Refinery produces, non-amine method synthesis, n (SiO2)/n(Al2O3)=27) use
NH4Cl solution exchanges washing to Na2O content is less than 0.2 weight %, filters to obtain filter cake；Take above-mentioned molecular sieve 100g (butt) plus water
The weight of solid content 10 % molecular sieve pulp is configured to, 390g hydrochloric acid (mass fraction 10%) is added in stirring；It is warming up to 65 DEG C of perseverances
Temperature stirring 1h, filtering are washed to filtrate neutrality；By filter cake plus water be beaten solid content be 40 weight % molecular sieve pulps, add
2.4gH3PO4(the weight % of concentration 85), be uniformly mixed with dipping, drying, 550 DEG C of calcination process 2 hours.Obtain molecular sieve DA2, materialization
Property data is listed in table 1.
Comparative example 3
By ZSM-5 molecular sieve, (catalyst asphalt in Shenli Refinery produces, non-amine method synthesis, n (SiO2)/n(Al2O3)=27) use
NH4Cl solution exchanges washing to Na2O content is less than 0.2 weight %, filters to obtain filter cake；Take above-mentioned molecular sieve 100g (butt) plus water
The weight of solid content 10 % molecular sieve pulp is configured to, 670g fluosilicic acid (mass fraction 3%) is added in stirring, adds the time
30min；65 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to filtrate neutrality；By filter cake plus water be beaten solid content is 40 heavy %
Molecular sieve pulp, add 2.4gH3PO4(the weight % of concentration 85), be uniformly mixed with dipping, drying, 550 DEG C of calcination process 2 hours.
Molecular sieve DA3 is obtained, physico-chemical property data are listed in table 1.
Comparative example 4
By ZSM-5 molecular sieve, (catalyst asphalt in Shenli Refinery produces, non-amine method synthesis, n (SiO2)/n(Al2O3)=27) use
NH4Cl solution exchanges washing to Na2O content is less than 0.2 weight %, filters to obtain filter cake；Take above-mentioned molecular sieve 100g (butt) plus water
The weight of solid content 10 % molecular sieve pulp is configured to, oxalic acid 20g is added in stirring, then by 200g hydrochloric acid (mass fraction 10%)
Add, add time 30min；65 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to filtrate neutrality；Filter cake plus water, which are beaten, to be consolidated
Content is 40 weight % molecular sieve pulp, adds 2.4gH3PO4(the weight % of concentration 85), uniformly it is mixed with dipping, dries, 550 DEG C of roastings
Burn processing 2 hours.Molecular sieve DA4 is obtained, physico-chemical property data are listed in table 1.
Comparative example 5
By ZSM-5 molecular sieve, (catalyst asphalt in Shenli Refinery produces, non-amine method synthesis, n (SiO2)/n(Al2O3)=27) use
NH4Cl solution exchanges washing to Na2O content is less than 0.2 weight %, filters to obtain filter cake；Take above-mentioned molecular sieve 100g (butt) plus water
The weight of solid content 10 % molecular sieve pulp is configured to, oxalic acid 20g is added in stirring, then by 334g fluosilicic acid (mass fractions
3%) it is slowly added to, adds time 30min；65 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to filtrate neutrality；By filter cake plus water
Be beaten solid content be 40 weight % molecular sieve pulps, add 2.4gH3PO4(the weight % of concentration 85), uniformly it is mixed with dipping, dries
Dry, 550 DEG C of calcination process 2 hours.Molecular sieve DA5 is obtained, physico-chemical property data are listed in table 1.
Comparative example 6
By ZSM-5 molecular sieve, (catalyst asphalt in Shenli Refinery produces, non-amine method synthesis, n (SiO2)/n(Al2O3)=27) use
NH4Cl solution exchanges washing to Na2O content is less than 0.2 weight %, filters to obtain filter cake；Take above-mentioned molecular sieve 100g (butt) plus water
The weight of solid content 10 % molecular sieve pulp is configured to, by 200g hydrochloric acid (mass fraction 10%) and 334g fluosilicic acid (matter under stirring
Measure fraction 3%) cocurrent addition, add time 30min；65 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to filtrate neutrality；Will filter
Cake add water be beaten solid content be 40 weight % molecular sieve pulps, add 2.4gH3PO4(the weight % of concentration 85), uniformly mixing leaching
Stain, drying, 550 DEG C of calcination process 2 hours.Molecular sieve DA6 is obtained, physico-chemical property data are listed in table 1.
Comparative example 7
By ZSM-5 molecular sieve, (catalyst asphalt in Shenli Refinery produces, non-amine method synthesis, n (SiO2)/n(Al2O3)=27) use
NH4Cl solution exchanges washing to Na2O content is less than 0.2 weight %, filters to obtain filter cake；Take above-mentioned molecular sieve 100g (butt) plus water
The weight of solid content 10 % molecular sieve pulp is configured to, is slowly added to 1332g fluosilicic acid (mass fraction 3%) under stirring, is added
Time 30min；65 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to filtrate neutrality；By filter cake plus water be beaten solid content be 40
Weight % molecular sieve pulp, adds 1.5gH3PO4(the weight % of concentration 85), uniformly it is mixed with dipping, dries, 550 DEG C of calcination process 2
Hour.Molecular sieve DA7 is obtained, physico-chemical property data are listed in table 1.
Embodiment 2
By ZSM-5 molecular sieve, (catalyst asphalt in Shenli Refinery produces, non-amine method synthesis, n (SiO2)/n(Al2O3)=27) use
NH4Cl solution exchanges washing to Na2O content is less than 0.2 weight %, filters to obtain filter cake；Take above-mentioned molecular sieve 100g (butt) plus water
The weight of solid content 10 % molecular sieve pulp is configured to, citric acid 40g is added in stirring, then by 100g sulfuric acid (mass fractions
10%) added with 500g fluosilicic acid (mass fraction 3%) cocurrent, add time 30min；It is warming up to 45 DEG C of constant temperature stirring 1h, mistake
Drainage is washed till filtrate neutrality；By filter cake plus water be beaten solid content be 40 weight % molecular sieve pulps, add 2.0gH3PO4(concentration
85 weight %), be uniformly mixed with dipping, drying, 550 DEG C of calcination process 2 hours.Molecular sieve B is obtained, physico-chemical property data are listed in table 1.
Embodiment 3
By ZSM-5 molecular sieve, (catalyst asphalt in Shenli Refinery produces, non-amine method synthesis, n (SiO2)/n(Al2O3)=27) use
NH4Cl solution exchanges washing to Na2O content is less than 0.2 weight %, filters to obtain filter cake；Take above-mentioned molecular sieve 100g (butt) plus water
The weight of solid content 10 % molecular sieve pulp is configured to, ethylenediamine tetra-acetic acid 10g is added in stirring, then by 1000g fluosilicic acid (matter
Measure fraction 3%) stream addition, time 30min is added, is eventually adding 400g hydrochloric acid (mass fraction 10%)；It is warming up to 85 DEG C of constant temperature
6h is stirred, filtering is washed to filtrate neutrality；By filter cake plus water be beaten solid content be 40 weight % molecular sieve pulps, add
1.6gH3PO4(the weight % of concentration 85), be uniformly mixed with dipping, drying, 550 DEG C of calcination process 2 hours.Obtain molecular sieve C, materialization
Prime number evidence is listed in table 1.
Comparative example 8
This comparative example explanation carries out P Modification processing using direct synthesizing high-silicon aluminum ratio molecular sieve.
By ZSM-5 molecular sieve, (catalyst Jian Chang branch companies produce, and have the synthesis of amine method, n (SiO2)/n(Al2O3)=210) use
NH4Cl solution exchanges washing to Na2O content is less than 0.2 weight %, filters to obtain filter cake；Take above-mentioned molecular sieve 100g (butt) plus water
Be beaten solid content be 40 weight % molecular sieve pulps, add 1.6gH3PO4(concentration 85%), dipping drying；Gained sample exists
550 DEG C of calcination process 2 hours, produce molecular sieve D.Physico-chemical property data are listed in table 1.
Embodiment 4-7 provides phosphorus aluminium inorganic binder used in the present invention.
Embodiment 4
The present embodiment prepares phosphorus aluminium inorganic binder of the present invention.
1.91 kilograms of boehmites (are contained into Al2O31.19 kilograms), 0.56 kilogram of kaolin (0.50 kilogram of butt) with
3.27 kilograms of decationizing water are beaten 30 minutes, and stirring adds 5.37 kilograms of concentrated phosphoric acids (mass concentration 85%) in descending toward slurries,
It is 0.04Kg phosphoric acid/minute/Kg alumina sources that phosphoric acid, which adds speed, is warming up to 70 DEG C, is then reacted 45 minutes at this temperature,
Phosphorus aluminium inorganic binder is made.Material proportion is shown in Table 2, obtains binding agent Binder1.
Embodiment 5-7
Method as described in embodiment 4 prepares phosphorus aluminium inorganic binder, and material proportion is shown in Table 2, obtains binding agent
Binder2-4。
Embodiment 8-13 provides the assistant for calalytic cracking of the present invention.
Embodiment 8
Molecular sieve-4 A, kaolin and boehmite are taken, decationized Y sieve water is added and Alumina gel is beaten 120 minutes, stirring
Lower addition FeCl3·6H2The O aqueous solution (FeCl3The weight % of content 30), the weight % of solid content 30 slurries are obtained, add hydrochloric acid
The pH value 3.0 of slurries is adjusted, then proceedes to mashing 45 minutes, then adds phosphorus aluminium inorganic binder prepared by embodiment 4, stirring
After 30 minutes, obtained slurries are spray-dried, microballoon is obtained, microballoon is calcined 1 hour at 500 DEG C, ZJ is made1, it is matched somebody with somebody
Than being shown in Table 3.
Embodiment 9
Molecular sieve-4 A, kaolin and boehmite are taken, decationized Y sieve water is added and Alumina gel is beaten 120 minutes, stirring
Lower addition ZnCl2The aqueous solution (the weight % of concentration 30), obtain the weight % of solid content 30 slurries, add hydrochloric acid regulation slurries
PH value is 3.0, is then beaten 45 minutes, is then charged with the phosphorus aluminium inorganic binder of the preparation of embodiment 7.The slurry that will be obtained
Liquid is spray-dried under conditions of 500 DEG C of dry gas inlet temperature, 180 DEG C of exhaust temperature, and microballoon is roasted at 500 DEG C
Burn 1 hour, auxiliary agent ZJ is made2.Auxiliary agent proportioning is shown in Table 3.
Embodiment 10
Molecular sieve-4 A and boehmite, kaolin are taken, decationized Y sieve water is added and Ludox is beaten 120 minutes, obtain
The weight % of solid content 35 slurries, adding hydrochloric acid makes the pH value 3.0 of slurries, is then beaten 45 minutes, is added into mixed serum
Embodiment 5 prepare phosphorus aluminium inorganic binder, stir 30 minutes, by obtained slurries be spray-dried, obtain microballoon, by microballoon in
It is calcined 1 hour at 500 DEG C.
Thus obtained microsphere product is taken, adds ZnCl2The aqueous solution, 60 DEG C are warming up under stirring, reacted 20 minutes at this temperature
Afterwards, by slurries vacuum filter, drying, then it is calcined 2 hours at 500 DEG C, obtains auxiliary agent ZJ3, its proportioning is shown in Table 3.
Embodiment 11
Molecular sieve-4 A, kaolin and boehmite are taken, decationized Y sieve water is added and Ludox is beaten 120 minutes, stirring
Lower addition ZnCl2The aqueous solution (the weight % of concentration 30), obtain the weight % of solid content 30 slurries, add hydrochloric acid regulation slurries
PH value is 3.0, is then beaten 45 minutes, is then charged with the phosphorus aluminium inorganic binder of the preparation of embodiment 6 and 7.It will obtain
Slurries be spray-dried under conditions of 500 DEG C of dry gas inlet temperature, 180 DEG C of exhaust temperature, by microballoon in 500 DEG C
Lower roasting 1 hour, is made microballoon product.
Thus obtained microsphere product 1 kilogram (butt) is taken, adds the ammonium dibasic phosphate aqueous solution that 10 kilograms of concentration are 5 weight %
In, 60 DEG C are warming up under stirring, after reacting 20 minutes at this temperature, by slurries vacuum filter, drying, then at 500 DEG C
Roasting 2 hours, auxiliary agent ZJ is made4, auxiliary agent proportioning be shown in Table 3.
Embodiment 12
Molecular sieve B and boehmite, kaolin are taken, decationized Y sieve water is added and Alumina gel is beaten 120 minutes, stirring
Lower addition Co (NO3)2·6H2The O aqueous solution (the weight % of concentration 30), obtains the weight % of solid content 30 slurries, is adjusted with hydrochloric acid
The pH value of slurries is 3.0, then proceedes to mashing 45 minutes, adds phosphorus aluminium inorganic binder prepared by embodiment 5, stirs 30 points
Clock, obtained slurries are spray-dried, microballoon is obtained, microballoon is calcined 1 hour at 500 DEG C, auxiliary agent ZJ is made5.Auxiliary agent is matched somebody with somebody
Than being shown in Table 3.
Embodiment 13
Molecular sieve C, kaolin and boehmite are taken, decationized Y sieve water is added and Alumina gel is beaten 120 minutes, under stirring
Add Ga (NO3)3The aqueous solution, obtain the weight % of solid content 30 slurries, adding hydrochloric acid makes the pH value of slurries be 3.0, continues to beat
Slurry 30 minutes, phosphorus aluminium inorganic binder prepared by embodiment 6 is added, then be beaten 30 minutes, then obtained slurries sprayed dry
It is dry, microballoon is obtained, microballoon is calcined 1 hour at 500 DEG C, auxiliary agent ZJ is made6.Auxiliary agent proportioning is shown in Table 3.
Comparative example 9
Assistant for calalytic cracking is prepared according to the method described in the embodiment 2 in CN102851058B.
By the kaolin of 2.85 kilograms (butt), 4.52 kilograms of (butt) ZSM-5 ((SiO under stirring2)/
(Al2O3)=110) molecular sieve, 5.03 kilograms of Ludox, 1.17 kilograms of concentrated phosphoric acids, 58.6 grams of iron chloride, 160 grams of potassium nitrate add
Into 18.54 kilograms of decationizing water, it is mixed with beating 2 hours, gained slurry solid content 30%.Slurries are after homogeneous, spray
Mist is molded, and 650 DEG C of saturated steams are handled 4 hours, obtain assistant for calalytic cracking DB0。
Under stirring condition, by 5 kilograms of assistant for calalytic cracking DB0It is added in 10.5 kilograms of decationizing water, adds nitre
14.6 grams of 109 grams of sour zinc and molybdenum pentachloride, carry out ion exchange 1h under the conditions of 95 DEG C of temperature, filtered, washing, in 120 DEG C
After drying, 1h is calcined at 500 DEG C.Obtain the assistant for calalytic cracking DB containing 45 weight % molecular sieves1。
Comparative example 10
Auxiliary agent is prepared as described in Example 8, is not both with molecular sieve DA1Substitute A, reference auxiliary agent DB is made2.Reference helps
Agent proportioning is shown in Table 4.
Comparative example 11
Auxiliary agent is prepared as described in Example 10, is not both with molecular sieve DA3Substitute A, reference auxiliary agent DB is made3.Reference helps
Agent proportioning is shown in Table 4.
Comparative example 12
Take molecular sieve DA7, kaolin and boehmite, add decationized Y sieve water and Ludox be beaten 120 minutes, stir
Mix lower addition ZnCl2The aqueous solution (the weight % of concentration 30), obtain the weight % of solid content 30 slurries, add hydrochloric acid regulation slurries
PH value be 3.0, then be beaten 45 minutes, be then charged with embodiment 6 preparation phosphorus aluminium inorganic binder.By what is obtained
Slurries are spray-dried under conditions of 500 DEG C of dry gas inlet temperature, 180 DEG C of exhaust temperature, by microballoon at 500 DEG C
Roasting 1 hour, obtains microballoon product.
Thus obtained microsphere product 1 kilogram (butt) is taken, adds the ammonium dibasic phosphate aqueous solution that 10 kilograms of concentration are 5 weight %
In, 60 DEG C are warming up under stirring, after reacting 20 minutes at this temperature, by slurries vacuum filter, drying, then at 500 DEG C
Roasting 2 hours, auxiliary agent DB is made4, auxiliary agent proportioning be shown in Table 4.
Comparative example 13
Prepare auxiliary agent as described in Example 12, be not both with molecular sieve D substitute B, and with embodiment 6 preparation phosphorus aluminium without
Phosphorus aluminium inorganic binder prepared by machine binding agent alternate embodiment 5, reference auxiliary agent DB is made5.Reference auxiliary agent proportioning is shown in Table 4.
The auxiliary agent that embodiment 14-19 is prepared using fixed fluidized-bed reactor as catalyst cracker using the present invention enters
Row catalytic cracking reaction, illustrate the catalytic cracking reaction effect of assistant for calalytic cracking provided by the invention.
Embodiment 14-19
Respectively by 30 grams of auxiliary agent ZJ1-ZJ6Carried out under the conditions of 800 DEG C, 100% steam atmosphere at the aging of 12 hours
Reason.Take the different amounts of ZJ through burin-in process1-ZJ6(the industrial trade mark is DVR-3's with different amounts of industrial FCC equilibrium catalysts
FCC equilibrium catalysts, 5) micro-activity is shown in Table to be mixed respectively.Catalyst mixture is loaded into small fixed flowing bed reactor
In, catalytic cracking (raw material oil nature is shown in Table 6) is carried out to military mixed three feedstock oils shown in table 6.Table 7, table 8 give used catalyst
Mixed proportion (weight ratio), reaction condition and the reaction result of mixture.
Comparative example 14-18 illustrates the situation using reference auxiliary agent by taking fixed fluidized-bed reactor as an example.
Comparative example 14-18
Catalytic cracking is carried out to same feedstock oil by the method in embodiment 14, the difference is that used catalyst is respectively
100% industrial FCC equilibrium catalysts, DB1-DB5With the mixture of industrial FCC equilibrium catalysts.Table 7, table 8 give used urge
Mixed proportion (weight ratio), reaction condition and the reaction result of agent mixture.
Single organic acid oxalic acid dealuminzation (DA1) and single inorganic acid HCl dealumination (DA2) it can be seen from data in table 1
And organic acid oxalic acid and two kinds of acid of inorganic acid hydrochloric acid compound (DA4) effectively can not all remove the Al in ZSM-5 molecular sieve, silicon
Aluminum ratio does not change substantially, and could obtain preferable dealuminzation effect after only having used fluosilicic acid.Fluosilicic acid is used alone to take off
During aluminium (DA3), the ZSM-5 molecular sieve of high silica alumina ratio can be obtained, but mesopore is less, strong acid in total acid proportion compared with
Low, B acid/L acid ratios are relatively low.Fluosilicic acid composite organic acid oxalic acid dealuminzation (DA5), can not equally obtain higher mesopore volume.
Fluosilicic acid composite inorganic acid HCl dealumination (DA6), though allow mesopore volume increased, strong acid in total acid proportion with
And B acid/L acid ratio is all be not as high as molecular sieve provided by the invention.It is simple also to can obtain higher silicon by raising fluosilicic acid dosage
The ZSM-5 molecular sieve (DA7) of aluminum ratio, but molecular sieve crystallinity loss is serious, mesopore proportion and acid distribution are not changed
It is kind.The present invention uses compound acid system, under three kinds of sour synergies, can ensure the premise of molecular sieve structure integrality
Under effectively improve molecular sieve silica alumina ratio, regulation aluminium distribution, improve mesopore proportion, improve acid distribution.
From table 7 and table 8 as can be seen that compared with auxiliary agent prepared by existing method, octane enhancing additive provided by the invention,
Ensure with the isomery hydrocarbon content in higher octane number, especially gasoline component to increase while yield of gasoline, alkene
It is basically unchanged with aromatic hydrocarbons, improves gasoline composition well, and then improve octane number bucket.
Table 1
* S represents embodiment, and D represents comparative example.
Table 2
Table 3
Table 4
Table 5
| Project | Industrial equilibrium catalyst DVR-3 |
| Micro- index living | 63 |
Table 6
| Project | Numerical value | Project | Numerical value |
| Density (20 DEG C)/(gcm-3) | 0.9104 | Boiling range/DEG C | |
| Refractive index (70 DEG C) | 1.4917 | Initial boiling point | 251 |
| Viscosity (80 DEG C)/(mm2·s-1) | 18.54 | 5% | 325 |
| Viscosity (100 DEG C)/(mm2·s-1) | 10.89 | 10% | 355 |
| Freezing point/DEG C | 38 | 30% | 416 |
| Carbon residue/% | 3.1 | 50% | 452 |
| Four component compositions/% | The end point of distillation | 544 | |
| Saturated hydrocarbons | 63.7 | Tenor/(μ gg-1) | |
| Aromatic hydrocarbons | 21.6 | Al | 0.6 |
| Colloid | 14.5 | Ca | 21.5 |
| Asphalitine | 0.2 | Fe | 16.4 |
| Element composition/% | Mg | 0.6 | |
| C | 86.12 | Na | 1.8 |
| H | 12.64 | Ni | 7.9 |
| S | 0.65 | V | 0.6 |
| N | 0.277 | Pb | 2.1 |
Table 7
Table 8
Claims (12)
1. a kind of assistant for calalytic cracking for improving octane number bucket, on the basis of the butt weight of the auxiliary agent, the auxiliary agent bag
Include with dry basis 10-75 weight % phosphorous MFI structure molecular sieve, it is inorganic with dry basis 3-40 weight % phosphorus aluminium
Binding agent, the weight of the 1-30 in terms of oxide % other inorganic binders, with dry basis 0-60 weight % the second clay,
With the weight of the 0.5-15 in terms of the oxide % metallic addition selected from least one of VIII race's metal and manganese, zinc, gallium；Its
In,
Described phosphorus aluminium inorganic binder is phosphorus aluminium glue and/or the phosphorus aluminium inorganic binder containing the first clay, contains first with described
On the basis of the phosphorus aluminium inorganic binder butt weight of clay, the phosphorus aluminium inorganic binder for containing the first clay is included with Al2O3Meter
15-40 weight % aluminium component, with P2O5Count 45-80 weight % phosphorus component and be more than 0 with dry basis and be no more than 40 weights
% the first clay is measured, and its P/Al weight ratio is 1.0-6.0, pH value 1-3.5, solid content is 15-60 weight %；
N (the SiO of the molecular sieve2)/n(Al2O3) it is more than 100；With P2O5Count and on the basis of the butt weight of molecular sieve, it is described
The phosphorus content of molecular sieve is 0.1-5 weights %；The Al distributed constants D of the molecular sieve meets：0.5≤D≤0.8, wherein, D=Al
(S)/Al (C), Al (S) represent the inside H in crystal face edge using the zeolite crystal of TEM-EDS methods measure apart from interior arbitrarily large
Aluminium content in 100 square nanometers regions, Al (C) are represented using crystal face described in the zeolite crystal of TEM-EDS methods measure
The outside H of geometric center is apart from interior any aluminium content for being more than 100 square nanometers regions, wherein the H is the crystal face edge
Point arrives the 10% of the crystal face geometric center distance；The ratio that the mesopore volume of the molecular sieve accounts for total pore volume is 15-30 bodies %；
The ratio that the sour amount of the strong acid of the molecular sieve accounts for total acid content is 60-80%, and the ratio between B acid acid amounts and L acid acid amounts are 20-100.
2. auxiliary agent according to claim 1, wherein, the molecular sieve n (SiO2)/n(Al2O3) it is more than 120；With P2O5Meter is simultaneously
On the basis of the butt weight of molecular sieve, the phosphorus content of the molecular sieve is 0.1-4 weights %；The Al distributed constants of the molecular sieve
D meets：0.55≤D≤0.75；The ratio that the mesopore volume of the molecular sieve accounts for total pore volume is 20-25 bodies %；The molecule
The ratio that the sour amount of the strong acid of sieve accounts for total acid content is 70-75%, and the ratio between B acid acid amounts and L acid acid amounts are 30-80.
3. auxiliary agent according to claim 1, wherein, the first described clay be selected from kaolin, sepiolite, concave convex rod,
At least one of rectorite, montmorillonite and diatomite；Second clay is selected from kaolin, metakaolin, diatomite, sea
At least one of afrodite, attapulgite, montmorillonite and rectorite；Described other inorganic matter binding agents are selected from the thin water aluminium of plan
At least one of stone, Alumina gel, silicon-aluminum sol and waterglass.
4. auxiliary agent according to claim 1, wherein, the metallic addition introduced in the form of metallic compound described in help
Agent, the metallic compound are selected from oxide, hydroxide, chloride, nitrate, sulfate, phosphate and organic compound
At least one of thing.
5. according to the auxiliary agent described in any one in claim 1-4, wherein, on the basis of the butt weight of the auxiliary agent, institute
Auxiliary agent is stated also to contain with P2O5Phosphorus additive of the meter no more than 5 weight %.
6. auxiliary agent according to claim 5, wherein, the auxiliary agent includes 8-25 weight % phosphorus aluminium inorganic binder, 20-
60 weight % phosphorous MFI structure molecular sieve, 10-45 weight % the second clay, 5-25 weight % other inorganic binders,
1.0-10 weight % metallic addition and 0-3 weight % phosphorus additive.
7. a kind of preparation method for the assistant for calalytic cracking for improving octane number bucket, this method include：
Phosphorous MFI structure molecular sieve, phosphorus aluminium inorganic binder and other inorganic binders are mixed, adds or is added without second and glue
Soil, it is beaten, spray drying；Wherein, metallic addition is introduced, introduces or does not introduce phosphorus additive；
On the basis of total butt weight of the preparing raw material of auxiliary agent, the preparing raw material of the auxiliary agent is included with dry basis 10-
75 weight % phosphorous MFI structure molecular sieve, with dry basis 3-40 weight % phosphorus aluminium inorganic binder, in terms of oxide
1-30 weight % other inorganic binders, with dry basis 0-60 weight % the second clay, the 0.5-15 in terms of oxide
The weight % metallic addition selected from least one of VIII race's metal and manganese, zinc, gallium, and including or do not include with P2O5
Phosphorus additive of the meter no more than 5 weight %；Wherein,
Described phosphorus aluminium inorganic binder is phosphorus aluminium glue and/or the phosphorus aluminium inorganic binder containing the first clay, contains first with described
On the basis of the phosphorus aluminium inorganic binder butt weight of clay, the phosphorus aluminium inorganic binder for containing the first clay is included with Al2O3Meter
15-40 weight % aluminium component, with P2O5Count 45-80 weight % phosphorus component and be more than 0 with dry basis and be no more than 40 weights
% the first clay is measured, and its P/Al weight ratio is 1.0-6.0, pH value 1-3.5, solid content is 15-60 weight %；
N (the SiO of the molecular sieve2)/n(Al2O3) it is more than 100；With P2O5Count and on the basis of the butt weight of molecular sieve, it is described
The phosphorus content of molecular sieve is 0.1-5 weights %；The Al distributed constants D of the molecular sieve meets：0.5≤D≤0.8, wherein, D=Al
(S)/Al (C), Al (S) represent the inside H in crystal face edge using the zeolite crystal of TEM-EDS methods measure apart from interior arbitrarily large
Aluminium content in 100 square nanometers regions, Al (C) are represented using crystal face described in the zeolite crystal of TEM-EDS methods measure
The outside H of geometric center is apart from interior any aluminium content for being more than 100 square nanometers regions, wherein the H is the crystal face edge
Point arrives the 10% of the crystal face geometric center distance；The ratio that the mesopore volume of the molecular sieve accounts for total pore volume is 15-30 bodies %；
The ratio that the sour amount of the strong acid of the molecular sieve accounts for total acid content is 60-80%, and the ratio between B acid acid amounts and L acid acid amounts are 20-100.
8. preparation method according to claim 7, wherein, the preparation process of the phosphorous MFI structure molecular sieve includes：
A, sodium form MFI structure molecular sieve is subjected to ammonium exchange, obtains ammonium and exchange molecular sieve；Wherein, handed in terms of sodium oxide molybdena and with ammonium
Change on the basis of total butt weight of molecular sieve, the sodium content that the ammonium exchanges molecular sieve is less than 0.2 heavy %；
B, it is gained ammonium exchange molecular sieve in step a is molten in the Compound-acid dealumination agent being made up of fluosilicic acid, organic acid and inorganic acid
Dealumination treatment is carried out in liquid, and after being filtered and being washed, obtains dealuminzation molecular sieve；
C, after the dealuminzation molecular sieve of gained in step b being carried out into P Modification processing and calcination process, the phosphorous MFI structure is obtained
Molecular sieve.
9. preparation method according to claim 8, wherein, also include the step of dealumination treatment described in step b：To first have
Machine is sour to exchange molecular sieve mixing with the ammonium, then fluosilicic acid and inorganic acid are exchanged to molecular sieve mixing with the ammonium.
10. preparation method according to claim 8, wherein, the condition of dealumination treatment is described in step b：With dry basis
The molecular sieve of gauge, fluosilicic acid, the weight ratio of organic acid and inorganic acid are 1：(0.02-0.5):(0.05-0.5):(0.05-
0.5)；Treatment temperature is 25-100 DEG C, and processing time is 0.5-6 hours；Organic acid described in step b is selected from ethylenediamine tetrem
At least one of acid, oxalic acid, citric acid and sulfosalicylic acid, inorganic acid are at least one in hydrochloric acid, sulfuric acid and nitric acid
Kind.
11. preparation method according to claim 8, wherein, the processing of P Modification described in step c includes：Will be selected from phosphoric acid,
At least one of ammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate phosphorus-containing compound is impregnated to molecular sieve and/or ion is handed over
Change；The condition of the calcination process includes：The atmosphere of calcination process is air atmosphere or steam atmosphere；Sintering temperature is 400-
800 DEG C, roasting time is 0.5-8 hours.
12. preparation method according to claim 7, wherein, the preparation of the phosphorus aluminium inorganic binder for containing the first clay
Step includes：
(1) alumina source, the first clay and water mashing, are dispersed into the slurries that solid content is 8-45 weight %；Described oxidation
Silicon source for can by the aluminium hydroxide and/or aluminum oxide of sour peptization, with the first clay of dry basis with Al2O3The oxidation of meter
The weight ratio of silicon source is (being more than 0-40):(15-40)；
(2), concentrated phosphoric acid is added according to P/Al=1-6 part by weight in the lower slurries obtained toward step (1) of stirring；
(3) slurries that step (2) obtains, are reacted into 15-90 minutes at a temperature of 50-99 DEG C.
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